CN105765014A - Transparent hydrophobic coating materials with improved durability and methods of making same - Google Patents

Transparent hydrophobic coating materials with improved durability and methods of making same Download PDF

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Publication number
CN105765014A
CN105765014A CN201480055028.3A CN201480055028A CN105765014A CN 105765014 A CN105765014 A CN 105765014A CN 201480055028 A CN201480055028 A CN 201480055028A CN 105765014 A CN105765014 A CN 105765014A
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silane
hydrophobic coating
coating material
methods according
acid
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CN201480055028.3A
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CN105765014B (en
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布赖恩·科恩
百德瑞斯·麦苏里亚
塔米·麦特洛克
阿莱娜·麦格雷戈
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Yueshen laboratory USA Co.,Ltd.
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Luna Innovations Inc
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3225—Polyamines
    • C08G18/325—Polyamines containing secondary or tertiary amino groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
    • C08G18/4269—Lactones
    • C08G18/4277—Caprolactone and/or substituted caprolactone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/71—Monoisocyanates or monoisothiocyanates
    • C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
    • C08G63/6952—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Abstract

Durable, transparent, inorganic-organic hybrid hydrophobic coating materials for glass, metal or plastic substrates are provided. The coating materials are generally an acid catalyzed condensation reaction product comprised of an organic polymeric silane (e.g., a polyol functionalized with a silane through a urethane linkage or a polyamine functionalized with a silane through a urea linkage, such as isocyanatopropyltrimethoxysilane or isocyanatopropyltriethoxysilane), an inorganic metal alkoxide (e.g., silicon alkoxides such as tetraethoxysilane or tetramethoxysilane) and a fluorinated silane (e.g., (3,3,3-trifluoropropyl)trimethoxysilane or nonafluorohexyltrimethoxysilane).

Description

Transparent hydrophobic coating material of durability with improvement and preparation method thereof
GOVERNMENT INTERESTS
The present invention is to be Nos. at the contract number authorized by USN's Air Warfare Center N68335-10-C-0523 (2765.01) and the Government support of N68335-12-C-0117 (2675.02) Under carry out.Government enjoys some rights and interests of the present invention.
Technical field
Embodiment disclosed herein is usually directed to coating material, particularly relates to transparent and hydrophobic coating Material.According to embodiment disclosed herein, described coating material show improvement to abrasion and corrode The durability of environment.
Background technology
Water dumping (watershedding) on such as automobile or aircraft windshield surface can affect department Machine or the pilot visual field the most in operation.Strengthen the conventional of surface water dumping ability Method is by reducing the hydrophobic surface treatments of windscreen surface energy, thus guides water at the glass that keeps out the wind Form the globule (bead up) on glass surface and tumble.Various types of surfaces process, such as, wax, Hydrophobic silicone polymer (asWaterproofing agent) or there is the highest contact angle (contact Angles) and the extremely low super hydrophobic coating being rolled off angle (roll off angles), be developed with Improve the hydrophobicity of glass, metal or polymer surfaces.But, surface known to these processes the most not Durable.
Kanagasabapathy et al.1United States Patent (USP) No.8,338,351 disclose a kind of have big On the surface of the contact angle of 165 degree, produce transparent, intimate transparent and translucent super hydrophobic be coated with The application composition of layer and technique, said composition comprises hydrophobic silsesquioxane nano-particle, institute State nano-particle and comprise adhesion promoter group and low-surface-energy group.
United States Patent (USP) No.8,187,707 of Van Benthem et al. discloses a kind of super hydrophobic and is coated with Layer, this coating shows the contact angle more than 140 degree, and it includes the granule of Fructus Rubi shape, described Granule includes primary granule and sticks to the secondary granule on described primary granule surface.
United States Patent (USP) No.6,340,502 of Azzopardi et al. discloses a kind of for hydrophobicity/oleophobic The compositions of property coating, said composition contains alkoxy silane and halogenated silanes, alkoxy silane and halogen At least in one molecular end, there is fluoridized group for silane each of which, also disclose this Coating is applied to the method in residuite.
Known can have with the example of the reagent of hydrophobic property/oleophobic property, such as EP0492417, Alkyl silane described in EP0492545 and EP0672779.According to these publications, this hydrophobic Layer can (alkyl-trilaho-or trialkoxy silane, its alkyl be at least from the organosilan containing fluorination Comprise a fluoridized group of end) solution obtain, be applied to base material with anhydrous organic solvent Surface.One of problem relevant with these coatings is durability and the corrosion resistance of these coatings, can To be proved by progressively coming off of these coatings, especially by the property of automobile windshield wiper Can be proved, this makes to reuse hydrophobic coating.
United States Patent (USP) No.6072018 of Wilkes et al. describe wearability inorganic/organic Hybrid Materials Formation, this material is by least one metal alkoxide and the silane-functionalised Organic substance of low-molecular-weight The colloidal sol of (such as, secondary amine or tertiary amine, aliphatic dihydroxy alcohol, aromatic diol or triol)- Gel (sol-gel) condensation reaction and formed.Material disclosed in this publication makes have isocyanates The compound functionalization of the low-molecular-weight of the silane of functionalization, this material is wearability, but is not Hydrophobic.
In this area, transparent hydrophobic coating still be there is a need to, with improve glass baseplate, polymeric substrate and The water dumping ability of metal base, this coating (such as, is contacting in abrasion or rugged environment After acid, alkali or organic solvent, rain or ultraviolet) it is durable.This required coating is greatly Being useful in the application of amount, these application include as windshield, solar panels, coating, electricity The transparent protective coating of sub-element etc..Embodiment disclosed herein is intended to improve the most required painting Layer.
Summary of the invention
Generally, coating material disclosed herein demonstrates the ruggedness of improvement, and wearability is resistance to molten Agent (such as water, oil, Hydrocarbon, jet fuel, solvent, diluted acid, diluted alkaline), rain proofness Can, resistance to salt water, anti-ultraviolet property, pliability, to multiple base material (include metal, glass, Plastics and coating surface) adhesive force.Therefore, this novelty in the embodiments described herein Transparent hydrophobic coating material show improvement abrasion or rugged environment in ruggedness, Environmental resistance and chemical proofing, which increase on glass baseplate, polymeric substrate and metal base Water dumping.
According to embodiment described herein, for glass baseplate, metal base or plastic basis material Durable, transparent, inorganic-organic hybridization hydrophobic coating material is typically acid catalyzed condensation reaction Product, this product is made up of organopolysilane, inorganic metal alkoxide and silicon fluoride.
Some embodiment can use silane-functionalised polyhydric alcohol or polyamines (such as polyurethane silanes or Polyureas silane) as organopolysilane.These silane-functionalised polyhydric alcohol it may be that such as, with The polycaprolactone polyol with 2～4 hydroxyls of isocyanate-terminated silane reaction, or tool There is the polyamines (such as diethylenetriamines) of at least two primary amine group or secondary amine groups.Preferably Ground, these organopolysilane mean molecule quantities are 50～10000g/mol.
According to some embodiments, metal alkoxide includes that at least one per molecule has at least one silylation Hydrolyzable compound, silylation formula Si (R1)x(R2)4-xRepresent, wherein, R1Represent C1-C8 Alkyl, epoxide group, vinyl, acrylic；R2Represent hydrolyzable alkoxyl or halogen radical Group；X is 0,1,2 or 3.It is preferably tetramethoxy-silicane and tetraethoxysilane.
Silicon fluoride can be formula be Rf1Si(R1)x(R2)3-xCompound, wherein, Rf1Represent the most complete Fluorination or the fluoridized fragment of part；R1Represent alkyl, hydrolyzable alkoxyl or halogen group； X is 0,1 or 2.Silicon fluoride can be double Silante terminated PFPE or the silane of fluorine end-blocking, Such as.(3,3,3-trifluoro propyl) trimethyl silane or nine fluorine hexyl trimethoxy silanes.
Organopolysilane and inorganic metal alkoxide in some embodiment are about 1:10 to about with weight ratio 10:1 exists.The content of silicon fluoride is about 0.0001-1wt.%.
Optionally, can also to contain metal oxide nanoparticles (wear-resisting to increase for coating material Property), and/or ultra-violet stabilizer (to increase anti-uv-ray), corrosion inhibiter is (anticorrosive to increase Property).
Coating material can as the coating being coated onto on base material (such as, glass, polymer or metal), And solidify on base material, form optically transparent hydrophobicity solidification coating.
Coating material can be by reaction under the conditions of acid catalyzed hydrolysis-condensation reaction containing organic poly-silicon The reactant mixture of alkane, inorganic metal alkoxide and silicon fluoride and prepare.Aqueous acid catalyst is generally with it Content be enough to the pH making reactant mixture and exists (such as, between about 2～4) below 5.Acid is urged Agent can be mineral acid or organic acid, such as, and hydrochloric acid, sulphuric acid, nitric acid and acetic acid.
After following currently preferred detailed description of illustrative embodiments is thought over, this These bright aspects and other side will be apparent from.
Detailed description of the invention
As mentioned above, according to embodiments described herein, for glass baseplate, gold Durable, transparent, the inorganic-organic hybridization hydrophobic coating material that belong to base material or plastic basis material lead to The acid catalyzed condensation reaction products being often made up of organopolysilane, inorganic metal alkoxide and silicon fluoride.
A. organopolysilane
The organopolysilane component of described coating material must include polyhydric alcohol or polyamines, described polyhydric alcohol (including but not limited to dihydroxylic alcohols, trihydroxylic alcohol, tetrahydroxylic alcohol, pentabasis alcohol etc.) is to pass through urethane bonds (urethane linkage) uses the silane (such as, isocyanate-terminated silane) of metal alkoxide functionalization, Described polyamines is the silane by urea bond metal alkoxide functionalization.Polyhydric alcohol and isocyanate-terminated Reaction between silane can be with the tin catalyst catalysis of such as dibutyl tin laurate etc.Also may be used To use deriving from of other, such as, the polyhydric alcohol of polyester, polyethers, Merlon etc..
In a preferred embodiment, polyhydric alcohol or polyamines are by urethane bonds or urea bond isocyanide respectively Perester radical propyl trimethoxy silicane (isocyanatopropyltrimethoxysilane) or NCO The silane of propyl-triethoxysilicane (isocyanatopropyltriethoxysilane) functionalization.
Polyurethane silanes can (described many based on polyhydric alcohol by different kinds of molecules, oligomeric or poly Unit alcohol have at least 2 hydroxyls, it is therefore preferable to 3 or 4 hydroxyls) polyethers or polyester make. Can use molecular weight is 50-10000g/mol, it is preferable that the polyhydric alcohol of 1000-2000g/mol. It is, for example possible to use trade name CAPA of commercializationTMPolyether polyol (purchased from Perstorp Company), or the trade name of commercializationPolyethers based on polyhydric alcohol is (purchased from Bayer Material Science)。
Typical polyester and polyether polyol include weight average molecular weight polycaprolactone within the above range Dihydroxylic alcohols or trihydroxylic alcohol, polyoxyethylene dihydroxylic alcohols or trihydroxylic alcohol, polypropylene dihydroxylic alcohols and trihydroxylic alcohol.Excellent Elect the polycaprolactone with following structure as:
Wherein, m+n+p=7～16 can use.
Selectively, can use anti-by urea bond with isocyanate-terminated silane in an identical manner The polyamines answered.Polyureas silane can from different kinds of molecules, oligomeric or polymerization polyamines (described often Individual polyamine molecule has at least 2 primary amine group or secondary amine groups, it is preferable that 3 or 4 Individual amine groups) prepare.Can use molecular weight is 50-10000g/mol, it is preferable that 100-1000g/mol Polyamines.Can use satisfactorily, such as, two sub-ethylene triamines or commercialization Amine (purchased from Huntsman Petrochemical Corporation), such asT-403 Polyetheramine
Terminology used in this article " polyamines ", refers to any containing two or more primary amines or two grades The aliphatic of amine functional group or aromatic compound.Polyamine compounds can contain any suitable bone Frame chain structure, including saturated or undersaturated, and straight chain, side chain or ring-type structure. Representational polyamines includes polyetheramine, such as, have a diamine of following structure:
Wherein x=2～70, it is preferable that x is 2～7.
Selectively, polyetheramine is the triamine with following structure:
Wherein n=0～5；X+y+z is 3～100.Preferably, n=1, x+y+z=5～6.
B. inorganic metal alkoxide
The inorganic metal alkoxide component of coating material includes at least one metal alkoxide, such as, based on Si, The metal alkoxide of Al, Ti, Zr etc..Preferably silicon alkoxide.Silicon alkoxide may also comprise monofunctional Organic group, such as, epoxide, alkyl, phenyl, vinyl, sulfydryl, methacrylic acid Salt etc., or double Silante terminated compound, such as, two (trimethoxy) silicon ethane can be included.
Preferably metal alkoxide includes that at least one per molecule at least contains a silica-based Si (R1)x(R2)4-x Hydrolyzable compound；Wherein R1Represent alkyl (such as, C1-C8, polymerizable groups is (such as, Epoxide, vinyl, acrylic acid), or other end contain other organic group (hydroxyl, Isocyanates, amino, mercaptan etc.) alkyl) alkyl；R2Represent hydrolyzable group (such as, Alkoxyl or halogen group, it is preferable that methoxyl group, ethyoxyl or chloro)；X is 0,1,2,3.Excellent Selection of land, metal alkoxide is tetraethoxysilane or tetramethoxy-silicane.
C. silicon fluoride
The example of representational fluorosilane compounds includes that formula is Rf1Si(R1)x(R2)3-xCompound, Wherein, Rf1Represent all or part of fluoridized fragment (such as, 3,3,3-trifluoro propyls, (perfluor fourth Base) ethyl, (perfluoro hexyl) ethyl, (perfluoro capryl) ethyl, perfluorododecyl, perfluor ten Tetraalkyl, 17 fluoro-1,1,2,2-tetrahydrochysene octyl groups, nine fluorine hexyls or 13 fluoro-1,1,2,2-tetrahydrochysene octyl groups)； R1Represent alkyl (such as, C1-C8, it is preferable that C1-C4One-level alkyl or secondary alkyl)；R2Table Show hydrolyzable group (such as, alkoxyl or halogen group, preferably methoxyl group, ethyoxyl or Chloro)；X is 0,1 or 2.
Preferably, using formula is Rf2[Q-C(R)2-Si(R1)x(R2)3-x]zFluorinated silicon compound, wherein Rf2Represent multivalence poly-(perfluoroalkyl) or poly-(perfluor oxyalkylene) fragment；Q represents organic bivalence Linking group (example includes amide, ether, ester or polyurethane linking group)；R1Represent alkyl (such as, C1-C8, preferably C1-C4One-level alkyl or secondary alkyl)；R2Represent hydrolyzable group；X is 0,1 or 2；R represents the alkyl of hydrogen or 1-4 carbon, and R group can be identical or different. Preferably, R is hydrogen.
Hydrolyzable group R2Can be identical or different, and the most under suitable condition (such as, under acidic aqueous conditions) can hydrolyze, in order to the silane compound of fluorination subsequently may be used There is condensation reaction.Preferably, hydrolyzable group produces under hydrolysising condition and can be condensed The group of reaction, such as silanol group.
Some embodiment have employed the fluorine of the silane including double Silante terminated PFPE or fluorine end-blocking SiClx component, such as, (3,3,3-trifluoro propyl) trimethoxy silane, nine fluorine hexyl trimethoxy silanes Etc..
D. metal oxide particle
Optionally, metal oxide particle can be used in coating formulation to give required character, example Such as wearability, electric property or optical property.It is, for example possible to use silicon dioxide, titanium dioxide, Zirconium oxide and/or the metal oxide particle of aluminium oxide.It is preferably silicon dioxide (SiO2).For optics Transparency, it is preferable that granule is less than 100nm, such as, between about 1nm-100nm.Preferably The spherical nanoparticle that particle size is diameter 1-10nm.If there is granule, included in preparation Granule up to about 50wt.%, be preferably between about 20wt.%-30wt.%, be based on total preparation Weight.
D. component and character
The component of preparation can change, and this depends on required final attribute, such as, pliability, hard Degree, wearability, transparency or other required physical property.Generally, in the formulation, polysilane 1:10-10:1 is may be about, preferably with the weight ratio of metal alkoxide or the metal alkoxide of functional organic It is about 3:1.In the formulation, the percentage by weight of the silicon fluoride of use is about 0.0001-1wt.%, preferably It is about 0.0005-0.001wt.%.
Coating material can by by inorganic and organic component and water and aqueous acid catalyst the most molten Agent (such as, isopropanol) mixes and prepares.Add aqueous acid catalyst to cause hydrolyzable silicon The hydrolysis of alkyl.Preferably acid catalyst includes mineral acid (such as, hydrochloric acid, sulphuric acid and nitric acid) Or organic acid (such as, acetic acid).Add enough acid catalysts, to be dropped by the pH of reactant mixture Low to less than 5, preferably pH is 2～4.
Silicon fluoride component can be introduced directly in the inorganic solution with organic component subsequently.Selectively, Fluorine component can carry out prehydrolysis with acidifying water in suitable solvent, and this process can be with and without The assistance of the surfactant of fluorine functionalization.Coating agent is by organic and inorganic and silicon fluoride component Hydrolysis and condensation reaction and prepare, produce by fluorine functionalization bonded for Si-O-Si organic- Inorganic network structure.
Therefore, the coating formulation obtained can mix in a solvent, or optionally, it is not necessary to Solvent and mix.If use solvent, solvent can be alcohols (methanol, ethanol, propanol, isopropyl Alcohol, butanol etc.) or other water-soluble solvent (such as: acetone).In said preparation, solid Concentration depends on the thickness required for final application or application process.But, typically, system Agent can contain the solid of 5wt.%-100wt.%, and preferred solid concentration is 15wt.%-25wt.%.
The solution of coating material can be applied to base material by using any convenient coating method, including Leaching, brush, flow coat, spray etc., the solidification of coating can complete within the scope of big temperature, and this depends on Required attribute, such as, wearability, pliability etc., or depend on the thermal limit coating base material. Coating can solidify within the temperature range of about 25 DEG C-150 DEG C, preferably from about 75 DEG C.Solidification temperature Can be adjusted according to the compatibility with base material.
The thickness of solidification coating can be in the range of about 0.5 micron-20 microns, preferably from about 1 micron-5 Micron.
Curing hydrophobic coating described herein demonstrates visual clarity.More precisely, This curing hydrophobic coating demonstrates the transparency of at least about 99.5% to visible ray, is preferably at least about The transparency of 100%.The transparency of visible ray is changed in mist and is less than by this curing hydrophobic coating 1%, preferably no more than 0.1%.
Hydrophobic coating described herein is applicable to multiple substrate coating, provides with Ei base material and increases The chemical proofing that adds, grease proofness, water proofing property, liquid/gas barrier, wearability, anticorrosive Property and water dumping ability.Suitably base material include but not limited to glass, metal (such as, aluminum and iron and steel), Plastics (such as, Merlon and acrylic acid), hardened cement, mixed earth or cement mortar, timber And painted surface.
By will be further understood that the present invention with reference to the non-limiting example of the following present invention.
Embodiment 1
The coating material comprising lower series preparation can be applied to 3/16 English with the coating of about 1-5 micron thickness On the polycarbonate substrate of very little thickness.Coating solidifies at a temperature of about 90 DEG C.Then the base material to coating Test, test contact angle, water dumping angle (watershed angle) and visual appearance and (comprise Lightness, mist degree and definition characteristic), and this coating base material is carried out with uncoated polycarbonate substrate Contrast.
Coating material preparation
The polyhydric alcohol of synthesizing silane functionalization:
Polycaprolactone polyol is weighed in glass drying oven clean, that be completely dried.At another In glass drying oven that is clean and that be thoroughly dried, weigh the isocynate silane (example of correct mol ratio As, polycaprolactone dihydroxylic alcohols needs to double the isocyanates of the molar equivalent of caproic acid lactone).Fill different The glass drying oven of cyanate covers blend rubber partition with blanket of nitrogen and seals.Polycaprolactone polyol Middle weighing catalyst (such as, dibutyl tin laurate).Relative to acid in isocyanates and poly-caproic acid The joint weight of polyhydric alcohol, the weight of catalyst is 0.1%.Subsequently, also this bottle is covered with blanket of nitrogen Son, blend rubber partition seals.
Polycaprolactone polyol and catalyst are arranged in ice bath stirring.Isocyanates is by slowly Be added dropwise to stirring caproic acid lactone-catalyst mixture in, use ortho-nitrogen air-flow control drop rate. Ice bath should be kept during dropping；This exothermic heat of reaction and ice bath reduce the probability that side reaction occurs. Once isocyanates is all added, along with ice bath melted, it is allowed to this reaction is warmed to room temperature.This reaction At least six hour to be stirred.Carbimide. can be detected by infrared spectrum (FTIR) Ester peak (～2270cm-1) decline.Once isocyanates reacts completely and its peak disappears, by poly-ammonia Ester silane is bottled, and it is covered with nitrogen.Bottle should be amber glass or other dark glass Glass, thus reduce exposure, because this may cause remaining catalyst discolouration.
Standard coating synthesizes:
First mixed silanes.The mol ratio of the inorganic silane of the organosilan of 0.4 mole and 0.6 mole is Typically.Add a small amount of silicon fluoride, less than the 0.5% of total coating formulation.Add in this mixture Enter the fluorine-containing surfactant suitable with silicon fluoride content.In system based on solvent, this can be more Mix silicon fluoride well.
Then, in silane mixture, solvent is added.The volume of solvent should be about total coating solution 50-80%, up to 90%, depends on required coating layer thickness.Representational solvent include isopropanol, Ethanol or 1-propanol.
After silane is completely dispersed in solvent, add acidifying water.Water should be acidified to 0.05-0.1M's Molar concentration, depends on required hydrolysis rate.Hydrochloric acid or nitric acid may be used for reducing aqueous solution PH.Add mol ratio and be enough to the acidifying water of alkoxyl on hydrolysising silane.
By coating solution mixing 1-2 hour, depend on the completeness of hydrolysis.Once silane is hydrolyzed, Before coating, by the filter filter coating material of 1 μm.Flow coat can be used, brush, spray or soak The method being coated with carries out coating application, to obtain best result.Once coat, it is allowed to unnecessary coating Tumble from base material before curing.At room temperature, coating surface drying (tack free) about 15 minutes.Can Selectively, coating can solidify 30-60 minute at 75-90 DEG C, to increase hardness and toughness.
Table 1: concrete coating formulation
A B
3-isocyanatopropyl silane 74.211g 74.211g
Capa 3050 polyether polyol 54.0g 54.0g
Dibutyl tin laurate 0.0641g 0.0641g
Tetraethoxysilane 35.8g 35.8g
Perfluoropolyether silanes 0.349g 0.349g
Isopropanol 461g 461g
IPA-ST silica gel 233g
0.05M HNO3 57.1g 57.1g
Table 2 shows getting rid of for selected coating base material, its water contact angle increased and reduction Water angle.
Table 2: for coating and uncoated base material, its water contact angle and water dumping angle
Table 3 shows the excellent optical properties of the base material of coating, does not lose transparency, mist degree Or definition (haze).
Table 3: coating and the optical properties of uncoated base material
Table 4 shows that coating provides the wearability of improvement to treated base material, and it is by more Low haze value is weighed.
Table 4: for coating and uncoated base material, the Taber abrasion impact on light transmission (ASTMD4060 500g/500 time；CS10F rotates (wheels))
Base material Transparency (%) Mist degree (%)
Merlon 89.0 35.0
Merlon coats A 90.5 4.9
Polyurethane 89.2 18.8
Polyurethane coats A 90.6 5.9
Acrylic acid 93.3 29.4
Acrylic acid coats A 93.8 4.2
Add silica gel (Nissan Chemical Snowtex IPA-ST) and can improve as shown in table 5 resistance to Mill property
Table 5: add the abrasive effect after silica gel: coating A contrasts coating B
Base material Coating A Coating B
Water contact angle 111° 112°
Water dumping angle 4° 4°
Transparency 93.6% 93.9%
Mist degree 0.33% 0.48%
Mist degree after 30 abrasions 2.93% 1.45%
Mist degree after 100 abrasions 3.59% 1.06%
Embodiment 2
The polyamines of synthesizing silane functionalization:
Polyamines (such as, diethylenetriamines) is weighed in glass drying oven clean, that be completely dried. Glass drying oven that is clean and that be completely dried weighs the isocynate silane of correct mol ratio at another (such as, diethylenetriamines needs to be three times in the molar equivalent of isocyanates).The glass of dress isocyanates Glass vessel blanket of nitrogen covers, and blend rubber partition seals.
Polyamines is arranged in ice bath stirring.The amine mixing that isocyanates is slowly dropped in stirring In thing, use ortho-nitrogen gas flow optimized drop rate.Ice bath is kept during dropping, because this reaction Heat release and ice bath can reduce the generation of side reaction.Once add all of isocyanates, because ice Bath is melted, it is allowed to reaction is raised to room temperature.At room temperature this reaction at least stirs six hours.By infrared Spectrum (FTIR) measures the decline of isocyanate peak (～2270cm-1).Once isocyanates is complete Reaction and peak disappear, and bottled polyureas silane also covers with nitrogen.
******************************
Although the present invention combines it is now recognized that the most practical and preferred embodiment are illustrated, but should
It is understood by the invention is not restricted to the disclosed embodiments, on the contrary, this invention is intended to contain bag
The various improvement being contained in the spirit and scope of the present invention and equivalence set.

Claims (33)

1. a hydrophobic coating material, produces including the acid catalyzed condensation reaction being made up of following material Thing:
Organopolysilane；
Inorganic metal alkoxide；And
Silicon fluoride.
Hydrophobic coating material the most according to claim 1, wherein said organopolysilane is silicon The polyhydric alcohol of alkane functionalization or polyamines.
Hydrophobic coating material the most according to claim 1, wherein said organopolysilane be with The polycaprolactone polyol containing two to four hydroxyls of isocyanate-terminated silane reaction.
Hydrophobic coating material the most according to claim 1, the poly-caproic acid of wherein said functionalization Lactone polyols molecular weight is 50～10000g/mol.
Hydrophobic coating material the most according to claim 1, wherein said organopolysilane is poly- Urea silane.
Hydrophobic coating material the most according to claim 5, wherein polyureas silane is containing at least The amine of two one-levels or secondary amine groups and the product of isocyanate-terminated silane.
Hydrophobic coating material the most according to claim 6, wherein said polyureas silane is two Asias Ethylene triamine and the product of isocyanate-terminated silane.
Hydrophobic coating material the most according to claim 7, wherein said metal alkoxide include to Few a kind of per molecule has the hydrolyzable compound of at least one silylation, described silylation formula Si(R1)x(R2)4-xRepresent, wherein R1Represent C1-C8Alkyl, epoxide group, vinyl, acrylic； R2Represent hydrolyzable alkoxyl or halogen group；X is 0,1,2 or 3.
Hydrophobic coating material the most according to claim 8, wherein said silicon fluoride is that formula is Rf1Si(R1)x(R2)3-xCompound, wherein, Rf1Represent all or part of fluoridized fragment；R1 Represent alkyl；R2Represent hydrolyzable alkoxyl or halogen group；X is 0,1 or 2.
Hydrophobic coating material the most according to claim 1, wherein said silicon fluoride is double silicon The PFPE of alkane end-blocking or the silane of fluorine end-blocking.
11. hydrophobic coating material according to claim 1, wherein said silicon fluoride is (3,3,3-trifluoro propyl) trimethoxy silane or nine fluorine hexyl trimethoxy silanes.
12. hydrophobic coating material according to claim 1, wherein said organopolysilane and Inorganic metal alkoxide is with weight ratio as 1:10～10:1 exists.
13. hydrophobic coating material according to claim 12, wherein said silicon fluoride is with content It it is 0.0001～1wt.% existence.
The base material of 14. 1 kinds of coatings, it includes base material and the coating on base material, wherein said coating It is made up of the hydrophobic coating material described in claim 1.
The base material of 15. coatings according to claim 13, wherein said base material be glass baseplate, Polymeric substrate or metal base.
The base material of 16. coatings according to claim 13, wherein said coating is at high temperature solid Change.
17. 1 kinds of methods preparing hydrophobic coating material, described method is included in acid catalyzed hydrolysis Under the conditions of condensation reaction, reaction includes the reactant mixture of following material:
Organopolysilane；
Inorganic metal alkoxide；And
Silicon fluoride.
18. methods according to claim 17, wherein said organopolysilane is silane-functionalised Polyhydric alcohol or polyamines.
19. methods according to claim 17, wherein said organopolysilane is containing 2～4 The polycaprolactone polyol of individual hydroxyl and the product of isocyanate-terminated silane.
20. methods according to claim 17, the polycaprolactone of wherein said functionalization is polynary The molecular weight of alcohol is 50～10000g/mol.
21. methods according to claim 17, wherein said organopolysilane is polyureas silane.
22. methods according to claim 21, wherein said polyureas silane is containing at least 2 The amine of one-level or secondary amine groups and the product of isocyanate-terminated silane.
23. methods according to claim 22, wherein said polyureas silane is diethylenetriamines Product with isocyanate-terminated silane.
24. methods according to claim 23, wherein said metal alkoxide includes that at least one contains There is the hydrolyzable compound of at least one silane group, with formula Si (R1)x(R2)4-xPer molecule represents, Wherein R1Represent C1-C8Alkyl, epoxide group, vinyl, acrylic；Wherein R2Represent hydrolyzable Alkoxyl or halogen group；X is 0,1,2 or 3.
25. methods according to claim 24, wherein said silicon fluoride is that formula is Rf1Si(R1)x(R2)3-xCompound, wherein Rf1Represent all or part of fluoridized fragment, R1 Representing alkyl, hydrolyzable alkoxyl or halogen group, x is 0,1 or 2.
26. methods according to claim 17, wherein said silicon fluoride is double Silante terminated complete Perfluoroalkyl polyether or the silane of fluorine end-blocking.
27. methods according to claim 17, wherein said silicon fluoride is (3,3,3-trifluoropropyl Base) trimethoxy silane or nine fluorine hexyl trimethoxy silanes.
28. methods according to claim 17, wherein said organopolysilane and inorganic metal alcohol Salt is with weight ratio as 1:10～10:1 exists.
29. methods according to claim 28, wherein said silicon fluoride with content be 0.0001～ 1wt.% exists.
30. methods according to claim 17, carry out institute in the presence of being included in aqueous acid catalyst Stating reaction, the content of described acid catalyst be enough to make the pH of reactant mixture below 5.
31. methods according to claim 30, the pH of wherein said reactant mixture is 2～4.
32. methods according to claim 30, wherein said acid catalyst is mineral acid or has Machine acid.
33. methods according to claim 32, wherein said acid catalyst choosing free hydrochloric acid, sulfur The group that acid, nitric acid and acetic acid are constituted.
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